Vicinal substituted alkanes

ABSTRACT

MIXTURES OF INTERNAL POSITION ISOMERS OF VICINALLY DISUBSTITUTED LINEAR ALKANES WHEREIN THE ALKYL CHAIN CONTAINS FROM 15 TO 17 CARBON ATOMS AND THE SUBSTITUENTS ARE HYDROXY OR ALKOXY GROUPS, AT LEAST ONE OF THE SUBSTITUENTS BEING ALKOXY GROUPS, ARE EFFECTIVE SURFACTANTS.

United States Patent O 3,758,410 VICINAL SUBSTITUTED ALKANES Shih K.Lin, St. Louis, Mo., assignor to Monsanto Company, St. Louis, M0.

N Drawing. Continuation-in-part of applications Ser. No. 710,644, Mar.5, 1968, and Ser. No. 852,898, Aug. 25, 1969, both now abandoned. Thisapplication Apr. 21, 1971, Ser. No. 136,249

Int. Cl. Clld 3/075 U.S. Cl. 252-89 7 Claims ABSTRACT OF THE DISCLOSUREMixtures of internal position isomers of vicinally disubstituted linearalkanes wherein the alkyl chain contains from 15 to 17 carbon atoms andthe substituents are hydroxy or alkoxy groups, at least one of thesubstituents being alkoxy groups, are effective surfactants.

BACKGROUND OF THE INVENTION Field of the invention This application is acontinuation-in-part of US. patent application, Ser. No. 710,644, filedMar. 5, 1968 and US. patent application, Ser. No. 852,898, filed Aug.25, 1969, both of said applications now abandoned.

This invention relates to novel surfactant compositions and to detergentformulations containing such compositions as a surfactant component.

As is well known in the detergent industry, surfactants are compounds orcompositions, which in solution, are effective to remove dirt, soil,stains, etc., from fabrics and various other materials. Such surfactantscan be used alone or, more commonly, in combination with variousadjuvants, re-enforcers, supplements, augmentors, potentiators and/orbenefactors usually referred to as detergency builders which incombination with the surfactant provide formulations of enhancedcleansing ability.

An effective surfactant should exhibit substantial cleaning ability notonly for natural fabrics or fibers such as cotton but also syntheticfibers such as the polyesters and blends of synthetics with naturalfabrics such as the polyester/ cotton blends now utilized extensively inmany fabrics.

'In order to avoid contamination of natural water supplies, it isfurther desirable that a surfactant be biodegradable. Further, from thestandpoint of economy and, in some instances, ecological consideration,it is desirable that a surfactant exhibit effective cleaning power incombination with relatively small amounts of builder components. It isadditionally desirable that the surfactant have a relatively high flashpoint in order to permit safe utilization in conventional detergentformulation procedures such as spray drying and low volatility toprevent loss and air pollution. Obviously, it is essential that asurfactant for commercial utilization be economically producible incommercial volumes.

Many surfactants and particularly certain polyglycol ethers are known tothe detergent industry as surface active agents. For example, there isdisclosed in US. Pat. 2,671,811 a 1,12-octadecanediol/ethylene oxidecondensate which is suggested for use as an anti-foaming agent. InBritish Pat. 1,041,036, there are disclosed various terminal polyglycolether compounds which are suggested as having utility as cleansingagents. In US. Pat. 3,119,- 848, there is disclosed a9,10-octadecanediol/ ethylene oxide condensate which is suggested foruse as a surface active agent.

Although many surfactants are known, the number suitable forcommercialization is quite limited in view of the fact that manysurfactants are not efiective on a variety 3,758,410, Patented Sept. 11,1973 of fabrics, are not suitable for incorporation into detergentformulations by preferred commercial processes, are non-biodegradable,or are not economically producible. It is apparent, therefore, that theprovision of novel surfactants possessing the essential commercialrequisites discussed above fulfils a recognized need in the detergentindustry.

Accordingly, it is an object of the present invention to provide novelsurfactants. A further object of the invention is to provide novelsurfactants which exhibit acceptable detergency on both natural andsynthetic fibers. A further object of the invention is to provide novelsurfactants which are biodegradable and exhibit good detergencycharacteristics even when combined with only relatively low amounts ofdetergency builders. Still another object of the invention is to providenovel detergent formulations based on such surfactants. I The inventionwill be better understood from the following description of thepreferred embodiments.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The novel surfactantcompositions of this invention are mixtures of internal position isomersof vicinally disubstituted linear alkanes having alkyl chain lengths offrom 15 to 17 carbon atoms. The vicinal substituents may be OH or O(C HO) H wherein x is 2 or 3 (preferably 2) and n is a number from 1 to 16with the proviso that at least one of the vicinal substituents is Theoverall degree of alkoxylation will be such that n averages from 3 to10, preferably 3 to 9, more preferably 5 to 9 and more preferably 5 to7. The mixture will contain at least 3 position isomers each present inan amount greater than 2 mole percent of the vicinally disubstitutedalkane of which it is an isomer as distinguished from a homologconsisting essentially of one isomeric form but containing trace amountsof other isomers. In the specification and claims, the term positionisomer is used to indicate compounds of the same alkane chain lengthhaving diiferences in positions of substituents on the alkane chain,even in the case where the substituents diifer so that under strictnomenclature the compounds would be designated as different rather thanas isomers. Thus, for example, a condensate of 3,4 hexadecanediol withone molecular proportion of ethylene oxide and a condensate of 5,6hexadecanediol with ten molecular proportions of ethylene oxide areconsidered herein as position isomers rather than merely differentcompounds. The term mixture of isomers is not, however, intended toencompass mixtures of homologs each present in only one isomeric form.That is, a composition of 2,3; 3,4; 4,5; etc., disubstituted dodecane isconsidered a mixture of isomers regardless of the nature of thesubstituents whereas a composition of 3,4 disubstituted dodecane; 4,5disubstitued undecane and 2,3 disubstituted tetradecane is not considered a mixture of isomers. Of course, the term encompasses acombination of mixed isomers of one homolog with mixed isomers ofanother homolog.

Such mixtures give superior detergency on both cotton and polyesterblend fabrics. In addition, these mixtures have high flash points andlow volatility which facilitates their processing in conventional spraydrying operations. Likewise, these products have low foaming propertiesmaking them useful in heavy duty detergent formulations for automaticwashing machines where minimum amounts of foam are desired. Moreover,they are readily prepared at economical cost.

To provide the advantages of this invention, a mixture of isomers, asdefined, must be utilized. It is found that such mixtures as compared tosingle isomers of vicinally disubstituted alkanes of the chain lengthspecified provide unexpected advantages in terms of performance inlaundry operations. The alkane chain length is additionally critical inthis respect since the unexpected advantage obtained by the use ofisomer mixtures is not observed in comparisons of performance of isomermixtures and single isomers of vicinally disubstituted alkanes havingalkyl chain lengths outside the above described range.

As previously pointed out, the surfactants of this invention may be amixture of isomers of vicinally disubstituted alkanes of a single chainlength, that is, a single homolog. For example, the surfactant may be amixture of 2,3; 3,4; 4,5; etc., disubstituted hexadecane. More commonlyand preferably from an economical viewpoint, the surfactant will be amixture of position isomers of a plurality of homologs having alkylchain lengths of from 15 to 17--.carbon atoms.

In the interest of the economy and to avoid the need of rigorousseparation and isolation of internal isomers and the homolog rangespecified, the mixtures of this invention may be employed in conjunctionwith varying amounts of terminal (1,2, substituted) vicinallydisubstituted linear alkanes and/or with vicinally disubstituted linearalkanes having alkyl chain lengths greater or less than 15 to 17 carbonatoms. In addition homologs composed of only one isomeric form may bepresent. The presence of such extraneous material does not destroy theadvantages of this invention althoughmaximum performance may not berealized in view of the dilution effect." Accordingly, the presence ofsuch extraneous material is preferably limited to trace amount (lessthan 2%) or at least to amounts less than 50%, although the advantagesof the invention are often apparent in surfactant compositionscontaining as little as 10% of the isomer mixtures described.

The novel compositions of the present invention may be prepared in anumber of ways. For example, an epoxide may be hydrolyzed to a diol, orreacted with ethylene glycol to form a fl-hydroxy ethylene glycol ether,the resulting composition then being combined with the appropriateamount of ethylene oxide. Alternatively, the epoxide can be reacted withthe appropriate amount .of polyethylene glycol, making further reactionwith the ethylene oxide unnecessary. The epoxides may be obtained fromolefins, for example, internal olefins (which may contain minor amountsof alpha olefins) or mixtures of internal olefins and saturatedcompounds, preferably straight chain internal olefins containing 12 to20 carbon atoms or a mixture of straight chain internal olefins andparaflins containing about 12 to 20 carbon atoms and mixtures thereof bywell known methods such as described in Kirk and Othmer Encyclopedia ofChemical Technology, Second Supplement, pp. 325-346 (1960).

Internal vicinal diols may be obtained from the corresponding epoxides,for example, by hydrolyzing the epoxides to diols using formic acid andhydrogen peroxide. This procedure is described by Swern, Billen andScanalan, Journal of the American Chemical Society, 68, (15 04-1507,1946).

Propylene oxide, ethylene oxide or mixtures thereof as mentionedhereinbefore, is condensed in varying amounts with the individualcompounds comprising the mixtures of the present invention. Theindividual condensates making up the mixture may have an amount ofalkylene oxide content from about 1 molecular proportion to about 16molecular proportions. The mixtures of the individual condensates havean overall average alkylene oxide content of about 3 to about 10molecular proportions, preferably about 5 to about 9 molecularproportions. It is further to be understood that in the productsobtained in accordance with the foregoing, the alkylene oxide chain maybe distributed equally or unequally on the two hydroxyl groups of thehydrophobe. In this connection, the present invention is not meant to belimited to any specific distribution between the alkylene oxide chainand the internal linear hydrophobe.

Alternatively, ethylene glycol or polyethylene glyco (PEG) having theformula:

HOCH CH OCH CH 'OCH CH OH,

where n is a number from 0 to about 10 may be reacted with internalepoxides, or mixtures of internal epoxides and paratfins having carbonchain lengths of from about 13 to about 18 carbon atoms, to prepare thecompositions of the present invention as hereinbefore mentioned.

Generally, the reaction product of'the ethylene glycol and the epoxideis a fl-hydroxy mono-ethylene glycol ether. This ether may then bereacted With ethylene oxide to get the desired products of the presentinvention. Alternatively, if polyethylene glycol is used as the reactantwith the epoxide mixtures, further ethoxylation is not required.

It is noted that preparative procedures based on raw material havingalkyl chain lengths of 13 to 18 carbon atoms have been described. It is,of course, essential that such materials contain a substantial amount ofthe C C17 homologs which provide the advantages of this invention. Theuse of all C C homologs in preparatory procedures is desirable but issometimes economically impractical to obtain raw materials so severelylimited with respect to chain length.

Generally, when straight chain isomeric internal vicinal diols arecondensed with an average of about 3 to about 10 molecular proportionsof alkylene oxide, the final product contains some unreacted diol. Ifdesired, this unreacted diol may be removed by distillation. Ifdistillation is employed, some low ethylene oxide condensates are alsoremoved. One advantage of removal is an increase in the flash point ofthe final product. Flash point is determined by the ASTM, Cleveland OpenCup Method. For example, a straight chain isomeric internal vicinal diolhaving an average carbon chain length of about 16 to about 17 wascondensed with an average of about 3.5 molecular proportions of ethyleneoxide and the final product contained about 20% by weight of unreacteddiol. This product has a flash point of 415 F. By removing all but about2.5% by weight of the unreacted diol by distillation, the flash point isincreased to about 495 F. This is accomplished by distilling the productat a temperature of about 250 C. at a pressure of 5 mm. of mercury untilabout 2.5% by weight of diol is left.

The novel detergent formulations of this invention comprise theabove-described surfactant mixture of the invention in combination witha detergent builder.

The amount of surfactant present in the detergent formulations, can varydepending on the end product performance desired. However, it ispreferred that the range of detergent active to builder weight ratio befrom about 1:10 to about 10: 1, and more preferably from about 1:7 toabout 1:1. The detergent formulation should contain at least 2% byweight of the surfactant of this invention.

Any of the well known detergency builders employed in combination withconventional surfactants to provide enhanced cleansing performance canbe utilized. For example, alkaline water-soluble inorganic salts such astrisodium phosphate and tripotassium phosphate; dialkali metal hydrogenphosphates such as disodium hydrogen phosphate and dipotassium hydrogenphosphate; the alkaline water-soluble molecularly dehydrated alkalimetal phosphate salts such as the alkali metal pyrophosphates, forexample, tetrasodium pyrophosphate, tetrasodium hydrogen pyrophosphateand tetrapotassium pyrophosphate, also the alkali metaltripolyphosphates such as sodium tripolyphosphate (Na P O and potassiumtripolyphosphate; the water-soluble alkali metal metaphosphates such assodium hexametaphosphate; the water-soluble alkali metal silicates suchas sodium silicate having a Na O to SiO mole ratio of 1:1 to 1:3.6,preferably 1:1 to 1:35 and the corresponding potassium silicates; thewatersoluble alkali metal borates such as calcined sodium tetraborate orborax; and the water-soluble alkali metal carbonates or bicarbonatessuch as sodium or potassium carbonates; or sodium sulfate may beutilized.

Examples of organic builders that can advantageously be employed includethe amino polycarboxylic acids and salts such as the sodium potassiumand ammonium salts of nitrilotriacetic acid (trisodiumnitrilotriacetate), the sodium potassium and ammonium salts of amino tri(methylene phosphonic acid), as well as the free acid; and thediphosphonic acids and salts (methylene diphosphonic acid and l-hydroxy,ethylidene diphosphonic acid). There may also be included builders suchas the watersoluble salts of polymeric aliphatic polycarboxylic acidssuch as sodium polymaleate, sodium polyitaconate, sodium(itaconate-aconitrate) copolymer, sodium (itaconateacrylate) copolymer,sodium (ethylene-maleate) copolymer, sodium (ethylene-maleate) copolymer(crosslinked), sodium (vinylmethylether-maleate) copolymer, and sodium(isobutylene-maleate) copolymer as disclosed and described in U.S. Pat.3,308,067 which is incorporated herein by reference, a synergisticbuilder combination, as disclosed and described in U.S. Pat. 3,368,978,which is also incorporated herein by reference, and mixtures thereof.

An enzymatically active substance, i.e., a substance composed of asingle enzyme or a mixture of enzymes, may also be used in conjunctionwith the compositions of the present invention. Enzymatically activesubstances may be obtained from animals, plants or micro-organisms andit is preferred to use enzymatically active substances of a microbialorigin as they can be economically produced in appreciable amounts.Suitable micro-organisms produce either a single enzyme or :a mixture ofenzymes.

If desired, supplementary surfactants such as well known natural soapsor synthetic anionic, non-ionic, zwitterionic or amphoteric may beutilized. It is preferred, when using the supplemental actives, thatthere be a weight ratio of novel surface active compositions of thisinvention to the foregoing described supplementary actives of from aboutat least 1:1 to about 50:1.

The detergent formulations incorporating or embodying the novelcompositions of the present invention may contain any of the usualadjuvants, diluents and additives, for example, perfumes, antitarnishingagents, anti-redeposition agents, bacteria-static agents, dyes,fluorescent agents, suds builders, suds depressors, foam stabilizers andthe like.

The detergent formulations of the present invention can be prepared byany of the well known methods in order to yield desirable compositionforms such as bar, granular, flake, liquid and tablet forms. It is to beunderstood that this invention is not limited to any particular methodof preparing the detergent formulations containing the organic and/ orinorganic builder and the detergent-active (i.e., both the novelcompositions and supplemental detergent-actives). The builder, forexample, may be mechanically mixed, or slurried or dissolved in asolution of the other ingredients of the formulations. In addition, thedetergent-active (as heretofore defined) may be admixed with the builderin any of the forms in which the builder is present as well as beingadded simultaneously or separately to an aqueous solution containing thebuilder and/or other ingredients.

To more fully illustrate the subject invention, the following detailedexamples are presented. All parts, percentages and proportions are byweight unless otherwise indicated.

EXAMPLE I Five hundred grams of an alpha olefin having a carbon chainlength of carbon atoms and molecular weight of about 196 are chargedinto a one liter flask equipped with a thermometer, stirring apparatusand condenser. After heating up to 110 C., 100 grams of polystyrenesulfonic acid type cationic exchange resin, commercially available underthe trademark Amberlyst 15, is added and the resultant mixture stirredvigorously and kept at the above temperature for about 3 hours. At theend of this period, the alpha olefin is isomerized to a productcontaining internal olefins as verified by infrared absorption spectrum.The isomeric distribution of the product is given in Table I below. Fourhundred and fifty-six grams of this C isomerized product are thencharged to a distillation pot and fractionated through a S-plate, lOldershaw column. The fraction boiling at 118 through 180 C./l0millimeters of Water pressure is collected to yield a total ofsubstantially internal C olefin product of 405 grams. Into a two literround bottom flask equipped with a stirring apparatus, thermometer andcondenser are charged 124 grams of the isomerized C internal olefin, 845milliliters of an aqueous solution containing 97% by weight formic acidand 72 grams of an aqueous solution containing 30% by weight hydrogenperoxide. The heterogeneous resultant reaction mixture is heated whilestirring vigorously to 40 C. and held at that temperature for 24 hours.After this period, 605 milliliters of formic acid are stripped ofl"under reduced pressure. Six hundred milliliters of 3 N-methanolicpotassium hydroxide is then added and the resultant mixture refluxed forone hour. The excess methanol was stripped off under reduced pressure(i.e., 15 mm. of water) and then 900 milliliters of hot (70 C.)distilled water are added to the residue remaining in the pot. Afterstirring for 10 minutes, the resultant mixture is allowed to cool toroom temperature, i.e., 20 C. The lower water layer is then siphonedform the solid diol. A second portion of 900 milliliters of hot (70 C.)distilled water is added and the resultant mixture slurried. The mixtureis allowed to cool to room temperature, i.e., 20 C., and the lower waterlayer siphoned from the solid diol. The solid diol product is filteredand dried under reduced pressure (i.e., 15 mm. of water) in a rotaryevaporator, to yield 158 grams of diol product. The diol is firstrecrystallized from methanolpetroleum ether and then slurried with coldpetroleum ether, filtered and dried. A total of grams of an isomericmixture of substantially pure C vicinal diols having molecular weight ofabout 230 is obtained. A 0.2 gram sample of the purified diol mixture isdissolved in 25 ml. of ethanol. This is analyzed by the periodictitration as described by S. Sigia Quantitative Organic Analysis ViaFunctional Groups, John Wiley and Sons, Inc., 1963, p. 39. The analysisshows better than 98% of vicinal diols. The isomeric distribution isdetermined by a method described in an article, Quantitative Recoveryand Programmed Temperature Gas Chromatographic Analysis of PeriodatePermanganate Oxidative Cleavage Products, Analytical Chemistry, 35, p.426 (1964), and is listed in Table I below.

Into a conventional vessel are added 15 grams of the C isomeric internalvicinal diols produced by the procedure set forth above, and 0.2 gram ofpotassium hydroxide. The resultant mixture was heated to approximatelyC. under a nitrogen atmosphere. Ethylene oxide is then introduced in aseries of stages so that the total pressure is continuously maintainedabout 15 to 20 cm. above atmospheric pressure, the reaction is stoppedafter an average of about 5-6 molecular proportions of ethylene oxide isadded.

TABLE I [Isomerized olefin and vicinal diol distribution in percent] C15vicmal Cw vicinal C 1 vicinal 8,9 3 2 2 4. 5 Q in The above procedure isrepeated with 500 grams each of C and C Isomeric distribution of therespective olefins and the resulting vicinal diols is given in Table I.

EXAMPLE II Five hundred grams of a mixture of straight chain alphaolefins, of about 20% C 40% C 30% C and 10% C having an average carbonchain length of about 16 to about 17 carbon atoms and an averagemolecular weight of 231 are isomerized in a manner set forth in Example-I and then converted to the corresponding diol having a molecularweight of 265. One fifteen grams sample is ethoxylated in the samemanner as described in Example I with an average of 4-5 molecularproportions of ethylene oxide. The mixtures are tested for their foamingproperties, biodegradability properties and detergency characteristics.The forming properties are tested using the Ross-Miles procedure. Acommercial alcohol ethoxylate is also tested. The results are listed inTable II below.

The mixture of the present invention and the primary alcohol ethoxylatesare tested for biodegradability employing a two step procedure involvingthe sequential use of two commonly accepted microbiological techniques.The shake flask technique is used as the presumptive step in theprocedure. If a detergent-active is 90% or more degraded in thepresumptive step, no further testing is needed. If it is not degraded atleast 80%, it is considered to be not adequately biodegradable. However,if its biodegradability falls between 80% and 90% by the PresumptiveTest, its biodegradability must be determined by the Confirming Test.The confirming step is the semi-contiunous activated sludge test whichmore closely simulates sewage treatment plant operation. A material mustbe degraded at least 90% under this procerdure to be consideredadequately biodegradable. Both tests are conducted. They are more fullydescribed in Journal of the American Oil Chemists Society, 42, pp.986-993 (1965). A bismuth iodide method for analysis was employed asdescribed in Z. Anal. Chem. 196, pp. 251-259 (1963).

The results of the Presumptive Tests show that isomeric internal averageC C vicinal diol plus an average 4-5 E0. is 95% removed, and the primaryalcohol plus 13 E0. is 90%-95% removed. The results of the ConfirmingTest show that isomeric internal average C -C vicinal diol plus anaverage 4-5 ED. is 90%-95% removed, and the primary alcohol plus 13 ED.is 95%-100% removed.

The detergency of these mixtures and a C primary alcohol ethoxylate onpolyester cotton (65% cotton 35% polyester) and cotton fabrics aredetermined by employing a test more fully described in an article in theJournal of the American Oil Chemists Society, vol. 42, pp. 723-727,August 1965. The conditions of the wash Water are (a) a hardness of 150parts per million, (b) a detergency concentration of 0.2%, (c) atemperature of 49 C. and (d) a pH of 9 to 10, the test made using aterg-o-meter machine on standard soiled polyester cotton and cottonfabrics. The following detergent compositions are used in the tests withthe percentage being by weight in the aqueous washing solution.

8 Detergent active (a) or (b) .030 Sodium tripolyphosphate .10 Sodiumsilicate .020

(a) Isomeric internal average C16C17 vicinal diol plus an average of 4-610.0.; (b) C13 primary alcohol plus 14 10.0.

The results of using the above detergent formulation are given in TableIII.

TABLE III ARd . Polyester Active Cotton cotton Isomeric internal average015-01.; vicinal diol plus an average of 4-5 E.O 25 22. 2 C13 primaryalcohol plus E.O 24. 1 19 A gram sample of a straight chain isomericinternal vicinal diol, having an average carbon chain length of 16 to 17carbon atoms condensed with an average of 4 to 5 molecular proportionsof ethylene oxide products of Ex ample III, having 12 weight percent ofunreacted diol, is distilled at a temperature of 225 C. and a pressureof 0.15 mm. of mercury until about 1 weight percent of un reacted diolremained. The flash point determined by the ASTM method before removingthe diol is 430 F.; after removal, it is 510 F.

The detergency of the compositions of this invention stripped ofunreacted diol versus the unstripped composition and linear alkylbenzenesulfonate is determined using the same washing procedure as in ExampleIII. The water is characterized by having (a) hardness of parts/million,(b) a detergency concentration of 0.15%, (c) a temperature of 49 C. and(d) a pH of 9 to 10. The following detergent compositions are used inthe tests with the percentages being by weight in the aqueous washingsolution.

Formulations 1) Detergent active (a) or (b) 1 .022 Sodiumtripolyphosphate .06 Sodium silicate 015 (2):

Stripped isomeric internal average C -C diol plus an average of 4 13.0..015 Sodium tripolyphosphate .06 Sodium silicate 015 1 (a) Isomericinternal average Clo-C17 diol plus an average of 45 ELO. unstripped; (h)LAS.

The results of using the above detergent formulations are given in TableIV.

TABLE IV Active: Appearance loss Isomeric internal average C C diol plusan average of 4-5 R0. stripped 5.0 LAS 8.0 Isomeric internal average C-C diol plus an avererage of 4-5 unstripped 8.0

The soil removal is recorded as appearance loss because ten shirts thatwere cut into swatches for these starches were very different in theirinitial reflectance and hues. The lower the appearance loss, the betterthe performance of the formulation. As can be seen, the

EXAMPLE IV A straight chain isomeric internal C vicinal diol condensedwith an average of 3 molecular proportions of E0. prepared in the samemanner as Example I, a straight chain isomeric internal C vicinal diolcondensed with an average of 3 molecular proportions of E0. prepared inthe same manner as Example I, a straight chain isomeric internal Cvicinal diol condensed with an average of 3 molecular proportions of E0.prepared in the same manner as Example I, and a straight chain isomericinternal'average C -C vicinal diol condensed with an average of 3molecular proportions of ED. prepared in the same manner as Example Iwere tested for their detergency on polyester cotton fabrics. The testprocedure is the same as set forth in Example H. The water ischaracterized by having (a) a hardness of 150 parts/million, (b) adetergency concentration of 0.2=by weight based on the total weight ofthe water, (c) a temperature of 49 C. and (d) a pH of 9 to 10. Thefollowing detergent compositions are used in the test with thepercentages being by weight in the aqueous washing solution.

Detergent active .03 Sodium tripolyphosphate .08 Sodiumnitrilotriacetate .04 Sodium sulfate I .04

The results of using the above detergent formulation are shown in TableV below:

Table V gives the readings taken on a Gardner Color Difierence Meter. Ascan be seen from the results set forth in Table V, a mixture ofdifferent homologs gives better performance than does any one homologabove alone.

EXAMPLE V The following detergent formulations listed in Table VI givegood detergency on polyester as well as polyester cotton fabrics.

TABLE VII Active: ARd C diol condensed with 7 molecular proportions ofethylene oxide according to Example I and having similar random isomerdistribution 15 C diol condensed with 7 molecular proportions ofethylene oxide according to Example I and having similar random isomerdistribution 19.5 C diol condensed with 7 molecular proportions ofethylene oxide according to Example I and having similar random isomerdistribution 17 1,2 disubstituted C alkane (7 molecular proportionsethylene oxide) 13.7 7,8 disubstituted C alkane (7 molecular proportionsethylene oxide) 7.5 1,2 disubstituted C alkane (7 molecular proportionsethylene oxide) 13 8,9 disubstituted C alkane (7 molecular proportionsethylene oxide) 14 1,2 disubstituted C alkane (7 molecular proportionsethylene oxide) 11 9,10 disubstituted C alkane (7 molecular proportionsethylene oxide) 12 Direct comparison and routine extrapolation of thedata presented in Table VlI indicate that for alkyl chain lengths lessthan 15 or greater than 17 carbon atoms single isomer (either terminalor internal) provide superior performance as compared to mixtures ofisomers. However, unexpectedly, within the alkyl chain length rangespecified for the compositions of this invention, mixtures of isomersare superior to single isomers.

What is claimed is:

1. A mixture of internal position isomers of a vicinally disubstitutedlinear alkane having an alkyl chain length of from 15 to 17 carbonatoms, the substituents being selected from the group consisting of --OHand -O(C H O),,H, x being a number from 2 to 3, n being a number from 1to 16, at least one of the substituents being O(C H O) H, n averagingfrom 3 to 10 in said mixture and said mixture comprising at least 3position isomers each present in an amount greater than 2 mole percentof said vicinally disubstituted alkane.

2. The composition of claim 1 wherein x is 2 and n averages from 3 to 9.

3. The composition of claim 2 wherein n averages from 5 to 7.

4. The composition of claim 1 wherein both of said substituents are O(CH O),,H.

TABLE VI [Detergent Formulations of the Present Invention-Percent byWeight] Sodium Sodium polypolyitacon- Active Amount MQNTA 1 STP 1 HEDP 3maleate ate NaSiOz NaOMC l NazSO Isomeric straight chain internal 015-01vicinal diol plus an average of 5-6 E.O 10 1 10 Isomeric straight chaininternal 01 -0 vicinal dlol plus an average of 8-9 E.0 10 1 10 Isomericstraight chain internal Cis-Cm vicinal diol plus an average of 7-8 15.0l0 1 10 Cut-C17 (1101 plus H E.() 10 1 19 D 10 1 19 D 10 1 19 1Trisodium nitrilotriacetate H10. 3 Sodium tripolyphosphate.

3 l-hydroxy-l, l-ethylideue diphosphonic acid. 4 Sodiumcarboxymethylcellulose.

EXAMPLE VI Detergent formulations containing 10% of the active indicatedin Table VII below; 40% sodium tripolyphosphate; 12% sodium silicate(112.4 ratio Na Ozsio and 38% sodium sulfate are prepared.

These formulations are used in 0.15% concentration to wash uniformlysoiled swatches of polyester/cotton fabric in water at 120 F., 300 ppm.hardness. Detergency results (ARd) are shown in Table VII.

5. The composition of claim 1 wherein one of said substituents is -OHand the other of said substituents is -O (C H O) H.

6. The composition of claim 1 wherein said composition contains aplurality of homologs having alkyl chain lengths of from 15 to 17 eachof said homologs comprising a mixture of position isomers and at least 2homologs each being present in an amount greater than 2 mole percent ofthe weight of the mixture.

7. A detergent formulation consisting essentially of, as a surfactant,at least 3% by weight of a mixture of internal positiontisomers of avicinally disubstituted linear alkane having an alkyl chain length offrom 15 to 17 Carbon atoms, vthe substituents being selected from thegroup consisting of -OH and O(C H O) H, x being a number from 2 to 3, nbeing a number from 1 to 16 and averaging from '3 to 10 in said mixture,at least one of the substituents being 0 (C H OHH, said mixturecomprising at least 3 position isomers each present in an amount greaterthan 2 mole percent of said vicinally disubstituted alkane and a water'soluble detergency builder, the ratio of surfactant to detergencybuilder being from about 10:1 to about, 1.10.

t l eferences Cited UNITED STATES PATENTS 10/ 1968-. Bla'ser-etYal.260-615 I 1/1964 Wrigley et a1. -2 260-404 3/1966 Johnson. a t

FOREIGN PATENTS 1 6/1965 Belgium.

10 LEON D. ROSDQL, Primary Examiner P E. WILLIS, Assistant ExaminerU.'S. Cl. X.R.

"W050 UNKTED STATES FATENT @FFECE seamen F eoneeefiioe Patent No.3,7589% m p 11, 1973 Inventofle) Shin K. Liu

It is certified that error mppeem m the eboveddemcified patent and thateeid Lettema Patent are he'mby marinated ea mm belw:

In column. 7, line 26, after "con-" insert therefor cen In column 10,line 1 delete "1.3.7" and insert therefor l5 5 '"o In column 11, line15, delete "1 10" and insert therefor 1:10

Signed and sealed this 16th day of April 197).

(SEAL) Attest:

EDWARD TIQFLETQEMELJIL Go l-TAHSHALL DELHJI Attesting OfficerCommissioner of Patents

